Hydration of Acetylene: A 125th Anniversary

Ponomarev, D. A.; Shevchenko, S. M.

doi:10.1021/ed084p1725

Cited by 29 publications

(16 citation statements)

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“…The hydration of acetylene to acetaldehyde catalyzed by mercuric salts was discovered by Kucherov already in 1881. 261 For many years this remained the main industrial process for the synthesis of acetaldehyde until more lucrative processes were invented. The advent of gold chemistry has recently opened up new mild routes toward hydration of alkynes (Scheme 43) for the production of aldehyde and ketone derivatives.…”

Section: Alkyne Hydrationmentioning

confidence: 99%

Water in N-Heterocyclic Carbene-Assisted Catalysis

et al. 2015

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Section: Alkyne Hydrationmentioning

confidence: 99%

Water in N-Heterocyclic Carbene-Assisted Catalysis

et al. 2015

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“…His discovery had a remarkable effect on the development of industrial chemistry as the catalytic addition of water to alkynes generates valuable carbonyl compounds from unsaturated hydrocarbon precursors, such as acetaldehyde from acetylene, and acetone from propyne [82]. Left C 2 H 2 (green) accommodated in a pocket within the hydrophobic ring (gray) at the end of the substrate channel right above the water molecule (red).…”

Section: Bio-inspired Tungsten Acetylene Complexesmentioning

confidence: 99%

Acetylene hydratase: a non-redox enzyme with tungsten and iron–sulfur centers at the active site

Kroneck

2016

J Biol Inorg Chem

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In living systems, tungsten is exclusively found in microbial enzymes coordinated by the pyranopterin cofactor, with additional metal coordination provided by oxygen and/or sulfur, and/or selenium atoms in diverse arrangements. Prominent examples are formate dehydrogenase, formylmethanofuran dehydrogenase, and aldehyde oxidoreductase all of which catalyze redox reactions. The bacterial enzyme acetylene hydratase (AH) stands out of its class as it catalyzes the conversion of acetylene to acetaldehyde, clearly a non-redox reaction and a reaction distinct from the reduction of acetylene to ethylene by nitrogenase. AH harbors two pyranopterins bound to W, and a [4Fe-4S] cluster. W is coordinated by four dithiolene sulfur atoms, one cysteine sulfur, and one oxygen ligand. AH activity requires a strong reductant suggesting W(IV) as the active oxidation state. Two different types of reaction pathways have been proposed. The 1.26 Å structure reveals a water molecule coordinated to W which could gain a partially positive net charge by the adjacent protonated Asp-13, enabling a direct attack of C2H2. To access the W-Asp site, a substrate channel was evolved distant from where it is found in other members of the DMSOR family. Computational studies of this second shell mechanism led to unrealistically high energy barriers, and alternative pathways were proposed where C2H2 binds directly to W. The architecture of the catalytic cavity, the specificity for C2H2 and the results from site-directed mutagenesis do not support this first shell mechanism. More investigations including structural information on the binding of C2H2 are needed to present a conclusive answer.

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“…- the Kucherov reaction, replaced by the Wacker process (also known as the Hoechst-Wacker process), i.e. method for the production of acetaldehyde via the direct oxidation of ethylene in an aqueous medium [ 11 ];…”

Section: Reviewmentioning

confidence: 99%

Upgrading oxygenated Fischer-Tropsch derivatives and one-step direct synthesis of ethyl acetate from ethanol - examples of the desirability of research on simple chemical compounds transformations

Klimkiewicz

2014

Chemistry Central Journal

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Oxygenates formed as by-products of Fischer-Tropsch syntheses can be transformed into other Fischer-Tropsch derived oxygenates instead of treating them as unwanted chemicals. One-step direct synthesis of ethyl acetate from ethanol is feasible with the use of some heterogeneous catalysts. Despite their apparent simplicity, both transformations are discussed as targeted fields of research. Furthermore, the two concepts are justified due to the environmental protection. Arguments regarding the Fischer-Tropsch process are focused on the opportunities of the utilization of undesirable by-products. The effective striving for their utilization can make the oxygenates the targeted products of this process. Arguments regarding the one-step direct synthesis of ethyl acetate underline the environmental protection and sustainability as a less waste-generating method but, above all, highlight the possibility of reducing the glycerol overproduction problem. The production of ethyl acetate from bioethanol and then transesterification of fats and oils with the use of ethyl acetate allows managing all the renewable raw materials. Thus, the process enables the biosynthesis of biodiesel without glycerine by-product and potentially would result in the increase in the demand for ethyl acetate.Graphical Abstract.Electronic supplementary materialThe online version of this article (doi:10.1186/s13065-014-0077-9) contains supplementary material, which is available to authorized users.

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Hydration of Acetylene: A 125th Anniversary

Cited by 29 publications

References 0 publications

Water in N-Heterocyclic Carbene-Assisted Catalysis

Water in N-Heterocyclic Carbene-Assisted Catalysis

Acetylene hydratase: a non-redox enzyme with tungsten and iron–sulfur centers at the active site

Upgrading oxygenated Fischer-Tropsch derivatives and one-step direct synthesis of ethyl acetate from ethanol - examples of the desirability of research on simple chemical compounds transformations

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